阅读说明：本技术 一种用于海洋无毒防污的有机硅改性聚脲及其制备方法 (Organic silicon modified polyurea for ocean non-toxic antifouling and preparation method thereof ) 是由 王宝柱 苏坤 宋丹 林旺 刘丽媛 于 2021-01-14 设计创作，主要内容包括：本发明提出了一种用于海洋无毒防污的有机硅改性聚脲及其制备方法,该聚脲涂料包括A组分和B组分,A组分包括多元醇、二甲基羟基硅油和多异氰酸酯；B组分包括端氨基聚醚、多元醇、偶联剂、扩链剂等。本申请的A组分二甲基羟基硅油和聚醚多元醇的羟基与异氰酸酯反应,硅氧基链段作为软段接到主链上,从而制备得到聚硅氧烷和脲基链段相结合的有机硅基聚脲,有机硅聚脲可以同时具有有机硅与聚脲两种材料独特的一系列优异的性能,既能克服聚硅氧烷材料在力学性能方面较差的缺陷,也可以改善聚脲的耐候性不好的缺点；与现有技术相比,本申请的有机硅改性聚脲与基底的粘结性能以及机械性能得到了提高,并且无毒,不会影响海洋生物及破坏环境。(The invention provides an organic silicon modified polyurea for ocean non-toxic and antifouling and a preparation method thereof, the polyurea coating comprises a component A and a component B, wherein the component A comprises polyalcohol, dimethyl hydroxyl silicone oil and polyisocyanate; the component B comprises amino-terminated polyether, polyol, a coupling agent, a chain extender and the like. According to the application, the hydroxyl groups of the component A, namely the dimethylhydroxysilicone oil and the polyether polyol, react with isocyanate, and the siloxane-based chain segment is connected to a main chain as a soft segment, so that the silicone-based polyurea combining polysiloxane and urea-based chain segment is prepared, the silicone-based polyurea can have a series of unique excellent performances of two materials, namely the silicone and the polyurea, and the defects that the mechanical property of a polysiloxane material is poor and the weather resistance of the polyurea is poor can be overcome; compared with the prior art, the organic silicon modified polyurea has improved bonding performance and mechanical performance with a substrate, is nontoxic, and cannot influence marine organisms and damage the environment.)

1. An organic silicon modified polyurea used for ocean nontoxic antifouling is characterized in that: the adhesive comprises a component A and a component B, wherein the component A comprises polyalcohol, dimethyl hydroxyl silicone oil and polyisocyanate; the component B comprises amino-terminated polyether, polyol, a coupling agent, a chain extender, a catalyst, a water scavenger and color paste.

2. The silicone-modified polyurea for use in marine non-toxic antifouling of claim 1, wherein: the mass content of the hydroxyl value in the dimethyl hydroxyl silicone oil is 6-9%, and the molecular weight of the dimethyl hydroxyl silicone oil is 500-2000.

3. The silicone-modified polyurea for use in marine non-toxic antifouling of claim 1, wherein: the chain extender is alpha, omega-aminopropyl disiloxane.

4. The silicone-modified polyurea for use in marine non-toxic antifouling of claim 1, wherein: the polyalcohol comprises one or more of polyoxypropylene diol, polytetrahydrofuran ether diol, polycaprolactone diol, polyester diol and polycarbonate diol.

5. The silicone-modified polyurea for use in marine non-toxic antifouling of claim 1, wherein: the polyisocyanate comprises one or more of diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, cyclohexane dimethylene diisocyanate, xylylene diisocyanate and 1, 4-cyclohexane diisocyanate.

6. The silicone-modified polyurea for use in marine non-toxic antifouling of claim 1, wherein: the amino-terminated polyether comprises a difunctional amino-terminated polyether or a trifunctional amino-terminated polyether.

7. The silicone-modified polyurea for use in marine non-toxic antifouling of claim 1, wherein: the coupling agent comprises one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, borate coupling agent, bimetallic coupling agent and phosphate coupling agent; the catalyst comprises one or more of bismuth isooctanoate, zinc isooctanoate, triethylene diamine, dimorpholinodiethyl ether, tetrabutyl titanate and tetraisopropyl titanate; the water scavenger comprises a molecular sieve.

8. The silicone-modified polyurea for use in marine non-toxic antifouling of claim 1, wherein: the mass ratio of the polyhydric alcohol, the dimethyl hydroxyl silicone oil and the polyisocyanate in the component A is (50-100): (10-50): (150-250);

the component B comprises (by mass) amino-terminated polyether, polyol, coupling agent, chain extender, catalyst, water scavenger and color paste at a ratio of (30-60): 20-50): 1-2): 20-40): 0-1): 1-5.

9. A method for preparing the organic silicon modified polyurea used for the non-toxic and antifouling marine according to any one of claims 1 to 8, which is characterized in that: the preparation method comprises the preparation of a component A and the preparation of a component B, wherein the preparation of the component A comprises the following steps: stirring and heating polyol, adding dimethyl hydroxyl silicone oil, dehydrating under vacuum, adding polyisocyanate, and reacting to obtain a component A;

the preparation of the component B comprises the following steps: and uniformly mixing the amino-terminated polyether, the polyol, the coupling agent, the chain extender, the catalyst, the water removing agent and the color paste, and filtering to obtain the component B.

10. The method of preparing silicone-modified polyurea for use in marine non-toxic antifouling as claimed in claim 9, wherein: and (2) stirring and heating the polyhydric alcohol, adding dimethyl hydroxyl silicone oil, dehydrating under vacuum, adding polyisocyanate, and reacting until the NCO content is 14-17% to obtain the component A.

Technical Field

The invention relates to the technical field of coatings, in particular to organic silicon modified polyurea for ocean non-toxic and antifouling and a preparation method thereof.

Background

A large number of animals, plants and microorganisms live in the ocean. In general, undesirable deposits resulting from the attachment of marine organisms to the surface of marine solid facilities are referred to as marine biofouling. Many marine animals such as barnacles, oysters, mussels, limestates and the like often adhere to and grow on the surfaces of underwater facilities such as ship bottoms, buoys, seacoasts, pipelines and the like to cause undesirable deposition, thereby bringing harm to scientific research activities of marine production. If marine organisms are attached to and grow at the bottom of the ship, the speed is reduced, the sailing resistance is increased, the bottom of the ship is corroded, and the ship body is damaged; the coating is attached to the surface of a metal solid to damage the protective coating on the surface of the metal and accelerate the corrosion speed of the metal; attached to the inner surface of the marine pipeline to reduce the volume of the pipeline or to block the pipeline. Marine biofouling poses serious hazards to coastal protection, marine transportation, fishery production and marine industrial production.

In the face of marine fouling, the surface of a marine structure is coated with a layer of antifouling paint for preventing marine organisms from attaching and growing, and the antifouling paint is the simplest, convenient and feasible antifouling method at present, and the growth and propagation of the marine fouling organisms are inhibited by active substances slowly and uniformly released from the paint. However, these antifouling paints contain biocides such as tin and copper, and although the toxic substances in the paints kill a large number of fouling organisms on the bottom of ships, they cause serious marine pollution.

On the other hand, the surface of the marine structure is coated with the organic silicon-based antifouling material at present, but the conventional organic silicon-based antifouling material has low mechanical strength, weak adhesion with the substrate and poor static antifouling capability, and the use of the organic silicon-based antifouling material is limited to a certain extent.

Based on the technical problems of the current marine antifouling paint, improvement on the technical problems is needed.

Disclosure of Invention

In view of the above, the invention provides an organic silicon modified polyurea used for marine non-toxic and antifouling and a preparation method thereof, and at least partially solves the technical problems in the prior art.

In a first aspect, the invention provides an organic silicon modified polyurea for ocean non-toxic and antifouling, which comprises a component A and a component B, wherein the component A comprises polyalcohol, dimethyl hydroxyl silicone oil and polyisocyanate; the component B comprises amino-terminated polyether, polyol, a coupling agent, a chain extender, a catalyst, a water scavenger and color paste.

Optionally, the organic silicon modified polyurea for marine non-toxic and antifouling comprises 6-9% of hydroxyl value in the dimethylhydroxysiloxane oil by mass, and the molecular weight of the dimethylhydroxysiloxane oil is 500-2000.

Optionally, the chain extender is alpha, omega-aminopropyldisiloxane.

Optionally, the polyol comprises one or more of polyoxypropylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, polyester glycol and polycarbonate glycol.

Optionally, the polyisocyanate comprises one or more of diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, cyclohexanedimethylene isocyanate, xylylene diisocyanate, and 1, 4-cyclohexanediisocyanate.

Optionally, the amino-terminated polyether comprises difunctional amino-terminated polyether or trifunctional amino-terminated polyether.

Optionally, the coupling agent comprises one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a borate coupling agent, a bimetallic coupling agent and a phosphate coupling agent; the catalyst comprises one or more of bismuth isooctanoate, zinc isooctanoate, triethylene diamine, dimorpholinodiethyl ether, tetrabutyl titanate and tetraisopropyl titanate; the water scavenger comprises a molecular sieve.

Optionally, the organic silicon modified polyurea for ocean non-toxic and antifouling comprises a component A, wherein the mass ratio of polyhydric alcohol to dimethyl hydroxyl silicone oil to polyisocyanate in the component A is (50-100): (10-50): (150-250);

the component B comprises (by mass) amino-terminated polyether, polyol, coupling agent, chain extender, catalyst, water scavenger and color paste at a ratio of (30-60): 20-50): 1-2): 20-40): 0-1): 1-5.

In a second aspect, the invention also provides a preparation method of the organic silicon modified polyurea for the marine non-toxic and antifouling, which comprises the preparation of the component A and the preparation of the component B, wherein the preparation of the component A comprises the following steps: stirring and heating polyol, adding dimethyl hydroxyl silicone oil, dehydrating under vacuum, adding polyisocyanate, and reacting to obtain a component A;

the preparation of the component B comprises the following steps: and uniformly mixing the amino-terminated polyether, the polyol, the coupling agent, the chain extender, the catalyst, the water removing agent and the color paste, and filtering to obtain the component B.

Optionally, the preparation method of the organic silicon modified polyurea for ocean non-toxic and antifouling comprises the steps of stirring and heating the polyhydric alcohol, adding the dimethyl hydroxyl silicone oil, dehydrating under vacuum, adding the polyisocyanate, and reacting until the NCO content is 14-17% to obtain the component A.

Compared with the prior art, the preparation method of the organic silicon modified polyurea for ocean non-toxic and antifouling has the following beneficial effects:

(1) according to the organic silicon modified polyurea for ocean non-toxic and antifouling, the component A is prepared by mixing dimethyl hydroxyl silicone oil with polyether polyol, the hydroxyl groups of the dimethyl hydroxyl silicone oil and the polyether polyol react with isocyanate, and a silicon-oxygen chain segment is connected to a main chain as a soft segment, so that the organic silicon-based polyurea combining polysiloxane and a urea-group chain segment is prepared, the organic silicon polyurea can simultaneously have a series of unique excellent performances of two materials of organic silicon and polyurea, the defect that the mechanical property of a polysiloxane material is poor can be overcome, and the defect that the weather resistance of the polyurea is poor can be improved; compared with the traditional organic silicon-based antifouling material, the organic silicon modified polyurea for the marine non-toxic antifouling has improved bonding performance and mechanical performance with the substrate, and the application range is enlarged; compared with the traditional antifouling paint containing biocides such as tin, copper and the like, the organic silicon modified polyurea used for the ocean nontoxic antifouling is nontoxic, does not influence marine organisms and damage the environment, and has high practical value;

(2) according to the organic silicon modified polyurea for ocean non-toxic and antifouling, chain extender alpha, omega-aminopropyl disiloxane is added into the component B, a siloxane-based chain segment and a polyurea bond form a block copolymer, and the controllability of the physical and mechanical properties of an elastomer can be realized according to the structure of an isocyanate compound and the proportion of the chain extender.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

An organic silicon modified polyurea for ocean nontoxic antifouling comprises a component A and a component B, wherein the component A comprises polyalcohol, dimethyl hydroxyl silicone oil and polyisocyanate; the component B comprises amino-terminated polyether, polyol, a coupling agent, a chain extender, a catalyst, a water scavenger and color paste.

In some embodiments, the dimethylhydroxysilicone oil has a hydroxyl number of 6 to 9% by mass and a molecular weight of 500 to 2000. The hydroxyl value and the molecular weight of the dimethyl hydroxyl silicone oil correspond to viscosity, the mass content of the hydroxyl value is 6-9%, and the molecular weight is 500-2000, so that reaction and construction are facilitated.

Specifically, dimethylhydroxysilicone oil 107 is actually used as dimethylhydroxysilicone oil.

In some embodiments, the chain extender is α, ω -aminopropyldisiloxane.

In some embodiments, the polyol comprises one or more of polyoxypropylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol, polyester glycol, polycarbonate glycol; the average molecular weight of the polyhydric alcohol is 400-1500.

In some embodiments, the polyisocyanate includes one or more of diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, cyclohexanedimethylene diisocyanate, xylylene diisocyanate, 1, 4-cyclohexanediisocyanate.

In some embodiments, the amino-terminated polyether comprises a difunctional amino-terminated polyether or a trifunctional amino-terminated polyether.

In some embodiments, the coupling agent comprises one or more of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a borate coupling agent, a bimetallic coupling agent, and a phosphate coupling agent; the catalyst comprises one or more of bismuth isooctanoate, zinc isooctanoate, triethylene diamine, dimorpholinodiethyl ether, tetrabutyl titanate and tetraisopropyl titanate; the water removing agent comprises a molecular sieve, and the specification of the molecular sieve is 3A or 4A.

In some embodiments, the mass ratio of the polyol to the dimethylhydroxysilicone oil to the polyisocyanate in the A component is (50-100): 10-50): 150-250;

the component B comprises (by mass) amino-terminated polyether, polyol, coupling agent, chain extender, catalyst, water scavenger and color paste at a ratio of (30-60): 20-50): 1-2): 20-40): 0-1): 1-5.

Based on the same inventive concept, the application also provides a preparation method of the organic silicon modified polyurea for the marine non-toxic and antifouling, which comprises the preparation of the component A and the preparation of the component B, wherein the preparation of the component A comprises the following steps: stirring and heating polyol, adding dimethyl hydroxyl silicone oil, dehydrating under vacuum, adding polyisocyanate, and reacting to obtain a component A;

the preparation of the component B comprises the following steps: and uniformly mixing the amino-terminated polyether, the polyol, the coupling agent, the chain extender, the catalyst, the water removing agent and the color paste, and filtering to obtain the component B.

In some embodiments, the a component is prepared by: stirring and heating the polyhydric alcohol to 95-105 ℃, adding dimethyl hydroxyl silicone oil, dehydrating for 5-7 h under vacuum, releasing the vacuum, cooling to below 50 ℃, adding polyisocyanate, reacting for 3-4 h at 90 ℃, measuring the-NCO value, and discharging to obtain the prepolymer A component.

In some embodiments, the isocyanate index of the A component and the B component is 1.05 to 1.10.

In some embodiments, the A component is obtained by adding dimethyl hydroxyl silicone oil after stirring and heating the polyhydric alcohol, dehydrating under vacuum, adding polyisocyanate, and reacting until the NCO content is 14-17%.

When the organic silicon modified polyurea for ocean non-toxic and antifouling is used, the component A and the component B are mixed according to the volume ratio of 1: 1-1.2 and then coated on the surface of a sample.

According to the preparation method of the organic silicon modified polyurea for the marine non-toxic and antifouling, the component A is prepared by mixing dimethylhydroxysilicone oil and polyether polyol, wherein the hydroxyl groups of the dimethylhydroxysilicone oil and the polyether polyol react with isocyanate, and a siloxane chain segment is connected to a main chain as a soft segment; chain extender alpha, omega-aminopropyl disiloxane is added into the component B, a siloxane chain segment and a polyurea bond form a segmented copolymer, and the physical and mechanical properties of the elastomer can be controlled according to the structure of the isocyanate compound and the proportion of the chain extender; the silicon oxygen group can form intermolecular hydrogen bond with the carbamido chain segment, thereby forming a physical crosslinking network as a transition phase between the soft segment and the hard segment, avoiding sharp micro phase separation caused by polarity difference of the two phases, leading the stress to be better transferred from the soft segment area to the hard segment area, and leading the tensile strength of the polymer which introduces the silicon oxygen group as a mixed chain segment to be greatly improved; the silicone-based polyurea is prepared by combining polysiloxane and urea-based segments, and the combination of the polysiloxane and the urea-based segments has different chemical structures and characteristics, so that the combination of the polysiloxane and the urea-based segments can show unique properties, and the unique excellent properties comprise; the polysiloxane has extremely low glass transition temperature and surface energy, good hydrophobicity, good oxidation resistance, good thermal stability and the like. Meanwhile, the carbamido has good adhesive force, excellent physical properties such as tensile strength, tearing strength and the like, and corrosion resistance; the organic silicon polyurea can simultaneously have a series of unique excellent performances of two materials of organic silicon and polyurea, not only can overcome the defect of poor mechanical property of a polysiloxane material, but also can improve the defect of poor weather resistance of polyurea; compared with the traditional organic silicon-based antifouling material, the organic silicon modified polyurea for the marine non-toxic antifouling has improved bonding performance and mechanical performance with the substrate, and the application range is enlarged; compared with the traditional antifouling paint containing biocides such as tin, copper and the like, the organic silicon modified polyurea paint for the ocean non-toxicity and antifouling is non-toxic, can not influence marine organisms and destroy the environment, and has very high practical value.

In order to better improve the problems of damage intolerance and poor static antifouling performance of the organic silicon-based antifouling material, the organic silicon-based polyurea is successfully prepared by optimizing the proportion of soft and hard sections of the organic silicon-based antifouling material on the basis of the prepared organic silicon modified polyurea for the marine nontoxic antifouling material, and the antifouling performance of a system is improved.

The following further illustrates the preparation of the silicone-modified polyurea for marine non-toxic antifouling of the present application in specific examples.

Example 1

A preparation method of organic silicon modified polyurea for marine non-toxic and antifouling comprises the preparation of a component A and the preparation of a component B, wherein the preparation of the component A comprises the following steps:

s1, stirring and heating 100 parts by weight of PTMEG1000 and 50 parts by weight of dimethyl hydroxyl silicone oil 107 to 95 ℃, dehydrating for 5 hours under vacuum-0.1 MPa, relieving the vacuum, cooling to below 50 ℃, adding 200 parts by weight of MDI-50, reacting for 4 hours at 90 ℃, measuring the-NCO value to be 14% after the reaction is finished, and discharging to obtain a component A;

the preparation of the component B comprises the following steps: the component B is prepared by putting 30 parts by weight of amino-terminated polyether D2000, 2 parts by weight of silane coupling agent A171, 35 parts by weight of chain extender alpha, omega-aminopropyl disiloxane, 0.1 part by weight of catalyst bismuth isooctanoate, 5 parts by weight of 3A molecular sieve and 1 part by weight of black color paste into a storage tank of a high-speed dispersion machine in sequence, stirring for 20min at room temperature, grinding by a sand mill, and filtering and packaging by a 200-mesh copper filter screen.

Example 2

A preparation method of organic silicon modified polyurea for marine non-toxic and antifouling comprises the preparation of a component A and the preparation of a component B, wherein the preparation of the component A comprises the following steps:

s1, stirring and heating 150 parts by weight of PTMEG1000 and 10 parts by weight of dimethyl hydroxyl silicone oil 107 to 95 ℃, dehydrating for 5 hours under vacuum-0.1 MPa, relieving the vacuum, cooling to below 50 ℃, adding 200 parts by weight of MDI-50, reacting for 4 hours at 90 ℃, measuring the-NCO value to be 14% after the reaction is finished, and discharging to obtain a component A;

the preparation of the component B comprises the following steps: the component B is prepared by putting 50 parts by weight of amino-terminated polyether D2000, 20 parts by weight of alpha, omega-aminopropyldisiloxane, 1 part by weight of titanate coupling agent KR-TTS, 0.1 part by weight of catalyst bismuth isooctanoate, 1 part by weight of 4A molecular sieve and 4 parts by weight of black color paste into a storage tank of a high-speed dispersion machine in sequence, stirring for 15min at room temperature, grinding by a sand mill, and filtering and packaging by a 200-mesh copper filter screen.

The non-toxic and antifouling organosilicon modified polyurea for the ocean prepared in the above examples 1-2 is prepared by mixing the component A and the component B according to the volume ratio of 1:1, uniformly mixing the components by a spraying machine, spraying the mixture on the surface of a steel plate to obtain a coating, placing the obtained coating in an environment with the temperature of (25 +/-2) DEG C and the humidity of (50 +/-5%), curing for 7 days, and testing the tensile strength, the water contact angle, the icing force, the tensile strength, the elongation at break and the tearing strength, wherein the results are shown in the following table 1.

TABLE 1 Properties of the coatings obtained in the different examples

Performance of	Example 1	Example 2
			Tensile strength (Mpa)	≥12	≥12
Water contact Angle (°)	140	120
			Icing power (N)	12	15
Tensile strength (Mpa)	22	19
			Elongation at Break (%)	350	450
Tear Strength (N/mm)	80	75

As can be seen from the above Table 1, the coating formed by the organosilicon modified polyurea for marine non-toxic and anti-fouling prepared by the method has good drawing strength, icing force, tensile strength, elongation at break and tearing strength, and the formed coating has good physical properties. Meanwhile, the coating formed by the prepared organic silicon modified polyurea for the marine non-toxic and anti-fouling is larger than 90 degrees, which indicates that the formed coating has good hydrophobicity.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.